Mixed oxides of transition metals, hydrotreatment catalysts obtained therefrom and preparation process

ABSTRACT

New sulfide metal catalysts are described, containing Ni, Mo and W, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by sulfidation of mixed oxide precursors, also new, characterized in that they comprise an amorphous phase and a wolframite isostructural crystalline phase, the crystallinity degree of said mixed oxides being higher than 0 and lower than 100%, preferably higher than 0 and lower than 70%. The catalysts of the invention are useful as hydrotreatment catalysts, and in particular as hydrodesulfurization, hydrodenitrogenation and/or hydrodearomatization catalysts.

New sulfide metal catalysts are described, containing Ni, Mo, W, anelement Z selected from Si, Al and mixtures thereof, obtained by thesulfidation of suitable precursors, wherein said precursors are new andare mixed oxides containing Ni, Mo, W, at least one element selectedfrom Si, Al and mixtures thereof, optionally containing an organiccomponent selected from a suitable nitrogenated compound N, an organicresidue R containing carbon and nitrogen, and a mixture of the residue Rand nitrogenated compound N.

Said mixed oxides are characterized in that they comprise an amorphousphase and a wolframite isostructural crystalline phase, thecrystallinity degree of these mixed oxides being higher than 0 and lowerthan 100%, preferably higher than 0 and lower than 70%.

Suitable preparation methods of these precursors are also described. Thecatalysts obtained by the sulfidation of these precursors can be used ashydrotreatment catalysts, in particular as hydrodesulfurization,hydrodenitrogenation and/or hydrodearomatization catalysts.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-G illustrate the XRD diffraction patterns of the samples of (A)Example 2, (B) Example 3, (C) Example 4, (D) Example 5, (E) Example 6,(F) Example 7, and (G) Example 8.

FIG. 2 illustrates the XRD diffraction pattern of comparative Example 9.

FIG. 3 illustrates the XRD diffraction pattern of the calcined sampledispersal P3.

FIG. 4 illustrates the ²⁷ AL MAS NMR analysis of the sample dispersalP3.

Since the beginning of the last century, it has been known thattransition metals are converted to catalytic materials of the TMS(“Transition Metal Sulfide”) type, in the presence of heavy oilfractions rich in sulfur. The work of M. Pier, Z. Elektrochem., 35(1949), 291 is particularly important after which TMS catalysts such asMoS₂ and WS₂, became the basis of modern catalysts supported on alumina,with Co or Ni as promoters.

TMS of the second or third transition series, such as RuS₂ and Rh₂S₃,have proved to be very active and stable catalysts in hydrotreatmentprocesses. As they are based on precious metals, however, theirapplication is not widely diffused in industry. In all refiningprocesses in which unitary hydrotreatment operations must be effected,whether they be hydrogenation or the removal of sulfur and nitrogen, thepreferred catalysts are therefore based on Mo and W. Furthermore, bothCo and Ni, or both, are used for promoting the activity of the catalyst.The promoter allows to obtain an increase in the catalytic activitywhich depends on the preparation details, the type of material and otherfactors, but which can reach a factor 10-12 times higher with respect tothat of a catalyst without a promoter (H. Topsoe, B. S. Clausen, F. E.Massoth, in Catalysis, Science and Technology, vol. 11, J. R. Andersonand M. Boudard Eds., (Springer-Verlag, Berlin 1996)).

This phenomenon is called synergic effect and implies that promoter andbase metal act together.

Due to increasingly strict regulations on gaseous emissions, however,resort must be made to even more active catalysts. In particular, indiesel fuel for motor vehicles, the recent European regulation requiresa sulfur content <10 ppm. In order to be able to pass below theselevels, catalysts must be found that are capable of decomposingcompounds which are particularly difficult to treat, such as stericallyhindered dibenzothiophenes. In addition, the catalyst must also beactive with respect to compounds containing other heteroatoms, nitrogenin particular, which tend to deactivate its functionality with respectto compounds containing sulfur.

A recent development relates to the application of catalysts whichcomprise a non-noble metal of Group VIII and two metals of Group VIB.Catalysts of this type and the their preparation are described, forexample, in patents JP 09000929, U.S. Pat. Nos. 4,596,785, 4,820,677,6,299,760, 6,635,599, U.S. 2007/0286781, EP 1941944. In particular, asfar as the preparations are concerned, JP 09000929 describes a processfor impregnation of an inorganic carrier with Co (or Ni), Mo and W. U.S.Pat. Nos. 4,596,785 and 4,820,677 describe co-precipitation techniquesof the relative sulfides, which therefore require process phases ininert atmospheres. U.S. Pat. Nos. 6,299,760 and 6,635,599 describeco-precipitation methods with the use of complexing agents, from aqueoussolutions heated to around 90° C. US 2007/0286781 also describes apreparation process for materials based on transition metals, usingco-precipitation techniques. In patent EP 1941944, co-precipitationtechniques are coupled with heating phases to relatively hightemperatures.

None of these processes, however, allows an accurate control on thestoichiometry of the final material.

EP 340868 describes a sol-gel process for the preparation of amicro-mesoporous silica and alumina gel, amorphous to X-rays, having aSiO₂/Al₂O₃ molar ratio within the range of 30 to 500, a surface areawithin the range of 500 to 1,000 m²/g and a pore volume ranging from0.3-0.6 ml/g.

U.S. Pat. No. 5,914,398 describes a sol-gel process for the preparationof a micro-mesoporous silico-alumina.

In patent EP 0972568, a sol-gel process is described for obtaining acatalyst containing molybdenum with a specific surface area ranging from20 to 400 m²/g and a Mo/Si molar ratio >0.2, exemplified up to 4.5. Thisis a specific catalyst for the isomerization of n-paraffins.

Patent application MI2009A001680 describes a particular calibratedsol-gel synthesis whereby mixed oxides containing suitable transitionmetals (TM) of groups VIII and VIB, and containing silicon and/oraluminium, can be prepared, even in a high MT/Si or MT/Al molar ratio,at the same time maintaining high values of the specific surface areaand total pore volume. The preparation of these mixed oxides passesthrough the synthesis of precursors containing a gelifying agent. Theseprecursors containing a gelifying agent and the mixed oxides obtainedtherefrom, possibly after forming, are transformed into the relativesulfides. The mixed oxides described in MI2009A001680 can be formedwithout a binder and have the general formula:X_(a)Y_(b)Z_(c)O_(d) .pCwherein X is selected from Ni, Co and mixtures thereof,

-   Y is selected from Mo, W and mixtures thereof,-   Z is selected from Si and Al and mixtures thereof,-   O is oxygen-   C is selected from:    -   a nitrogenated compound N,    -   an organic residue deriving from the nitrogenated compound N by        partial calcination,        wherein said nitrogenated compound N is selected from:-   a) a tetra-alkylammonium hydroxide having formula (I):    R^(I)R^(II)R^(III)R^(IV)NOH  (I)    -   wherein the groups R^(I), R^(II), R^(III) and R^(IV), equal to        or different from each other, are aliphatic groups containing        from 1 to 7 carbon atoms,-   b) an amine having formula (II)    R¹R²R³N  (II)    -   wherein    -   R¹ is a linear, branched or cyclic alkyl, containing from 4 to        12 carbon atoms, and R² and R³, equal to or different from each        other, are selected from H and linear, branched or cyclic alkyl,        containing from 4 to 12 carbon atoms, said alkyl can be equal to        or different from R¹,-   a, b, c, d are the number of moles of the elements X, Y, Z, O    respectively,-   p is the weight percentage of C with respect to the total weight of    the compound having formula (A),-   a, b, c, d are higher than 0,-   a/b is higher than or equal to 0.3 and lower than or equal to 2,-   (a+b)/c is higher than or equal to 0.3 and lower than or equal to    10, and preferably ranges from 0.8 to 10-   d=(2a+6b+Hc)/2 wherein H=4 when Z═Si    -   H=3 when Z═Al        and p is higher than or equal to 0 and lower than or equal to        40%.

US 2007/0084754 describes a bulk catalyst comprising nickel and tungstenoxides as main components. A second metal of group VIB can be present inthe synthesis suspension, in a quantity lower than 10% in moles withrespect to the total quantity of metals of group VIB. The bulk catalystobtained has a metastable hexagonal structure and an X-ray diffractionpattern with a single reflection between 58 and 65° (diffraction angle2θ) and main reflections between 32 and 36° and between 50 and 55°. Thebulk catalyst treated at high temperatures gives an orthorhombiccrystalline phase NiWO₄ identified in the databank of powder diffractionpatterns as nickel tungstate oxide (JCPDS-ICDD PDF card 15-0755 or72-1189 or 72-0480).

US 2009/0139904 relates to a bulk catalyst comprising nickel andmolybdenum oxides as main components. A second metal of group VIB can bepresent in the synthesis suspension, in a quantity of less than 10% inmoles with respect to the total quantity of metals of group VIB. Thebulk catalyst obtained has a metastable hexagonal structure and an X-raydiffraction pattern with reflections between 33 and 35° (diffractionangle 2θ) and 58-61°. The bulk catalyst treated at high temperaturesgives crystalline phases hypothetically identified as α-NiMoO4 andβ-NiMoO4.

Salamanca et al., Phys. Chem. Chem. Phys. 2009, 11, 9583-9591 describesthe hydrothermal synthesis of compounds with a wolframite-type structurehaving a trimetallic composition among which NiMo_(0.5)W_(0.5)O₄. Thesynthesis is effected by hydrothermal treatment at 473 K and leads tothe formation of a completely crystalline material.

L. Gonzáles-Cortés et al., Journal of Molecular Catalysis A: Chemical238 (2005) 127-134, describes the synthesis of a family of materialswith a wolframite isostructural CoNiW composition. These materials aretransformed into carbides and used as HDN catalysts.

Particular mixed oxides have now been found, containing a wolframiteisostructural crystalline phase, capable of controlled crystallinity,obtained by means of a specific preparation process, which, possiblyafter forming, generate, by sulfidation, catalysts which areparticularly active in hydrotreatment processes, and in particular inhydrodesulfurization, hydrodenitrogenation and/or hydrodearomatizationprocesses. These catalysts are capable of reducing the content ofaromatic compounds, by hydrodearomatization, and particularly aromaticpolynuclear (PNA) compounds, present in the cut that is treated: thehydrodearomatization takes place contemporaneously with thehydrodesulfurization and hydrodenitrogenation if sulfur and nitrogenimpurities are also present in the cut.

A first object of the present invention therefore relates to mixedoxides, indicated with the abbreviation OM, containing Ni, Mo, W, atleast one element selected from Si, Al and mixtures thereof, andpossibly containing an organic component C selected from a nitrogenatedcompound N, an organic residue R containing carbon and nitrogen, and amixture of the residue R and nitrogenated compound N, characterized inthat they comprise an amorphous phase and a wolframite isostructuralmonoclinic crystalline phase, the crystallinity degree of said mixedoxides being higher than 0 and lower than 100%, preferably higher thanor equal to 3% and lower than 100%.

Wolframite is a mineral consisting of mixed iron and manganesetungstate, having a monoclinic symmetry. An isostructural crystallinephase refers to a phase having the same type of geometric crystallinestructure but different chemical compositions.

In particular, an object of the present invention relates to mixedoxides comprising an amorphous phase and a wolframite isostructuralcrystalline phase, having a crystallinity degree higher than 0 and lowerthan 100%, having formula (I):Ni_(a)Y_(b)Z_(c)O_(d) .pC  (I)possibly formed without a binder,wherein Y is a mixture of Mo and W in a molar ratio Mo/W greater than0.1 and less than 10,

-   Z is selected from Si, Al and mixtures thereof,-   O is oxygen,-   C is an organic component selected from a nitrogenated compound N,    an organic residue R containing carbon and nitrogen, a mixture of    the residue R and nitrogenated compound N,-   said nitrogenated compound N being an amine having formula (A)    R¹R²R³N  (A)    wherein-   R¹ is a linear, branched or cyclic alkyl, containing from 4 to 12    carbon atoms, and-   R² and R³, equal to or different from each other, are selected from    H and linear, branched or cyclic alkyl, containing from 4 to 12    carbon atoms, said alkyl possibly being equal to or different from    R¹,-   a, c, d are the number of moles of Ni, Z, O, respectively,-   b is the sum of the moles of W and Mo-   p is the weight percentage of C with respect to the total weight of    the compound having formula (I),-   a, b, c, d are greater than 0-   a/b is greater than or equal to 0.6 and lower than or equal to 1.5,-   (a+b)/c is greater than or equal to 0.3 and lower than or equal to    10, and preferably ranges from 0.8 to 10-   d=(2a+6b+Hc)/2 wherein H=4 when Z═Si    -   H=3 when Z═Al

and p is greater than or equal to 0 and lower than or equal to 40%.

Preferably, the crystallinity degree of the mixed oxides of the presentinvention is greater than or equal to 3% and lower than 100%, even morepreferably greater than or equal to 6% and lower than or equal to 90%. Aparticularly preferred aspect is that the crystallinity degree of themixed oxides of the present invention is greater than or equal to 10%and lower than or equal to 90%.

The crystallinity degree of a mixed oxide of the present invention isgiven by the ratio(Ix/Istd)*100wherein:

-   Ix is the integrated intensity of the peak positioned at 30.90°±0.5°    of 2-theta selected in the X-ray diffraction pattern of the mixed    oxide containing nickel, molybdenum and tungsten of the present    invention;-   Istd is the integrated intensity of the peak positioned at    30.90°±0.5° of 2-theta selected in the X-ray diffraction pattern of    the same mixed oxide containing nickel, molybdenum and tungsten,    subjected to thermal treatment at 900° C.

The mixed oxides containing nickel, molybdenum and tungsten that arethermally treated at 900° C. are completely crystalline and wolframiteisostructural: said oxides having a crystallinity of 100% are then usedas reference for calculating the crystallinity of the mixed oxides ofthe present invention. Said completely crystalline oxides have the X-raydiffraction pattern indicated in FIG. 1 a.

In the mixed oxides of the present invention, with a controlledcrystallinity degree, coexist therefore an amorphous phase and awolframite isostructural crystalline phase, and the appropriatecalibration of the entity of the crystalline phase allows to obtainmaterials that after sulfidation provide particularly high catalyticperformances in hydrotreatment, and with a wide range, comprising, inaddition to hydrodesulfurization and hydro-denitrogenation, alsohydrodearomatization and reduction in the content of polynucleararomatic compounds (PNA) in the hydrocarbon mixtures treated.

The organic residue R contained in the mixed oxides of the presentinvention, comprising carbon and nitrogen, is the residue obtained fromthe nitrogenated compound N when the mixed oxide containing saidcompound N is subjected to thermal treatment.

According to a preferred aspect, in the mixed oxides having formula (I),Y is a mixture of Mo and W in a molar ratio Mo/W ranging from 0.2 to 9.

According to a preferred aspect, in the mixed oxides having formula (I),a/b ranges from 0.80 to 1.4, preferably from 0.95 to 1.4, even morepreferably from 0.98 to 1.3.

When the mixed oxides OM of the present invention contain an organiccompound C selected from a nitrogenated compound N, an organic residue Rcontaining carbon and nitrogen, or a mixture of the residue R andnitrogenated compound N, said component is preferably in a quantitygreater than 0 and less than or equal to 25% by weight.

Compounds having formula (I) formed without a binder refer to compoundshaving formula (I) in the form suitable for being used industrially in areactor and without adding a binder, i.e. without the use of a binder inthe forming process. All forming techniques without binders can be usedfor the purpose. Particular new forming techniques are describedhereunder.

The mixed oxides OM of the present invention are transformed into therelative sulfides, wherein said sulfides are new and active ashydrotreatment catalysts. In particular, the compounds having formula(I) are transformed into the relative sulfides, active as hydrotreatmentcatalysts, by means of sulfidation: the sulfide metal compounds, called(I)S, containing Ni, Mo and W, an element Z selected from Si, Al,mixtures thereof, and possibly an organic residue R, obtained bysulfidation of the precursor compounds having formula (I), possiblyformed without a binder, or precursors having formula (I) in the shapedform with a binder, are, in turn, new and represent a further object ofthe present invention.

Hydrotreatment refers to a process in which a hydrocarbon feed isconverted, in the presence of hydrogen, at a high temperature andpressure. During the hydrotreatment, various reactions can take place,for example, hydrogenation, isomerization, hydrodesulfurization,hydrodenitrogenation and hydrodearomatization, depending on thecatalytic system and operating conditions used. The sulfide catalysts ofthe present invention, in particular those obtained by sulfidation ofthe precursors having formula (I), are active in hydrotreatment andparticularly selective in hydrodesulfurization and hydrodenitrogenationreactions, and in the hydrodearomatization of aromatic compounds,especially polynuclear aromatic compounds.

A particular object of the present invention relates to new mixed oxideswhich can be used, after sulfidation, as hydrotreatment catalysts,comprising an amorphous phase and a wolframite isostructural crystallinephase having a crystallinity degree greater than 70% and lower than100%, having a general molar formula (I1):Ni_(a)Y_(b)Z_(c)O_(d)  (I1)possibly formed without a binder, wherein Y is a mixture of Mo and W inwhich the molar ratio Mo/W is greater than 0.1 and less than 10,

-   Z is selected from Si, Al and mixtures thereof,-   O is oxygen,-   a, c, d are the number of moles of Ni, Z, O, respectively, and are    greater than 0-   b is the sum of the moles of W and Mo, and is greater than 0-   a/b is greater than or equal to 0.6 and lower than or equal to 1.5,-   (a+b)/c is greater than or equal to 0.3 and lower than or equal to    10, and preferably ranges from 0.8 to 10,-   d=(2a+6b+Hc)/2 wherein H=4 when Z═Si    -   H=3 when Z═Al.

According to a preferred aspect, in the mixed oxides having formula(I1), Y is a mixture of Mo and W in a molar ratio Mo/W ranging from 0.2to 9.

According to a preferred aspect, in the mixed oxides having formula(I1), a/b ranges from 0.80 to 1.4, preferably from 0.95 to 1.4, and evenmore preferably from 0.98 to 1.3.

Said oxides (I1) preferably have a crystallinity degree greater than 70%and lower than or equal to 90%.

As previously indicated, the compounds having formula (I1) aretransformed into the relative sulfides by means of sulfidation: thesulfide metal compounds, indicated as (I1)S, containing Ni, Mo and W, anelement Z selected from Si, Al and mixtures thereof, obtained bysulfidation of the precursor compounds having formula (I1), possiblyformed without a binder, or compounds having formula (I1) in the shapedform with a binder, are, in turn, new and represent a further object ofthe present invention. These particular sulfide compounds are in turnactive as hydrotreatment catalysts, and particularly selective inhydrodesulfurization and hydrodenitrogenation reactions, and in thehydrodearomatization of aromatic compounds, especially polynucleararomatic compounds.

Another particular object of the present invention relates to new mixedoxides, useful, after sulfidation, as hydrotreatment catalysts,comprising an amorphous phase and a wolframite isostructural crystallinephase having a crystallinity degree greater than 0 and lower than orequal to 70%, having general formula (I2):Ni_(a)Y_(b)Z_(c)O_(d) .pC  (I2)possibly formed without a binder,wherein Y is a mixture of Mo and W in which the molar ratio Mo/W isgreater than 0.1 and less than 10,

-   Z is selected from Si and Al and mixtures thereof,-   O is oxygen,-   C is an organic component selected from a nitrogenated compound N,    an organic residue R containing carbon and nitrogen, a mixture of    the residue R and nitrogenated compound N,-   said nitrogenated compound N being an amine having formula (A)    R¹R²R³N  (A)    wherein-   R¹ is a linear, branched or cyclic alkyl, containing from 4 to 12    carbon atoms, and-   R² and R³, equal to or different from each other, are selected from    H and linear, branched or cyclic alkyl, containing from 4 to 12    carbon atoms, said alkyl possibly being equal to or different from    R¹,-   a, c, d are the number of moles of Ni, Z, O, respectively,-   b is the sum of the moles of W and Mo-   p is the weight percentage of C with respect to the total weight of    the compound having formula (I2),-   a, b, c, d are greater than 0-   a/b is greater than or equal to 0.6 and lower than or equal to 1.5,-   (a+b)/c is greater than or equal to 0.3 and lower than or equal to    10, and preferably ranges from 0.8 to 10-   d=(2a+6b+Hc)/2 wherein H=4 when Z═Si    -   H=3 when Z═Al

p is greater than 0 and lower than or equal to 40%.

A particularly preferred aspect is that in said oxides (I2), thecrystallinity degree is greater than or equal to 3 and lower than orequal to 70%, more preferably greater than or equal to 3 and lower thanor equal to 60%, even more preferably it ranges from 6 to 60%. Aparticularly preferred aspect is that the crystallinity degree of themixed oxides having formula (I2) is greater than or equal to 10 andlower than or equal to 50%.

According to a preferred aspect, in the mixed oxides having formula(I2), Y is a mixture of Mo and W in a molar ratio Mo/W ranging from 0.2to 9.

According to a preferred aspect, in the mixed oxides having formula(I2), a/b varies from 0.80 to 1.4, preferably from 0.95 to 1.4, evenmore preferably from 0.98 to 1.3.

Said oxides (I2) are preferably mesoporous, have a surface area,determined after thermal treatment at 400° C., higher than or equal to90 m²/g and a pore volume higher than or equal to 0.18 ml/g. Inaccordance with the IUPAC terminology “Manual of Symbols andTerminology” (1972), Appendix 2, Part I Coll. Surface Chem. Pure Appl.Chem., Vol. 31, page 578, wherein micropores are defined as pores havinga diameter smaller than 2 nm, mesopores are defined as pores having adiameter ranging from 2 to 50 nm, macropores are those having a diameterlarger than 50 nm, the mixed oxides of the present invention havingformula (I2) are mesoporous, and are characterized by an irreversibleisotherm of type IV. The average pore diameter is preferably within therange of 3 to 18 nm.

The compounds having formula (I2), preferably with a crystallinitydegree greater than 0 and lower than or equal to 70%, are alsotransformed into the relative sulfides by means of sulfidation: thesulfide metal compounds, indicated as (I2)S, containing Ni, Mo, W, anelement Z selected from Si, Al and mixtures thereof, possibly an organicresidue, obtained by sulfidation of the precursor compounds havingformula (I2), possibly formed without a binder, or compounds havingformula (I2) in the shaped form with a binder, are in turn new and are afurther object of the present invention.

These particular sulfide compounds are active as hydrotreatmentcatalysts, and particularly selective in hydrodesulfurization andhydrodenitrogenation reactions, and in the hydrodearomatization ofaromatic compounds, especially polynuclear aromatic compounds.

Compounds having formula (I1) and (I2) formed without a binder refer tocompounds having formula (I1) and (I2) in a form suitable for being usedin a chemical reactor, without the addition of a binder, i.e. withoutthe addition of a binder in the forming process: said forming withoutthe addition of a binder can be effected with any technique known toexperts in the field. Particular forming processes are describedhereunder and are a further object of the present invention.

According to what is described above, the family of precursors havingformula (I) is therefore composed of precursors having formula (I1) andprecursors having formula (I2), the latter containing an organiccomponent selected from a nitrogenated compound N having formula (A), anorganic residue R containing carbon and nitrogen, or a mixture thereof.

With reference to the mixed oxides OM of the present invention, and inparticular the oxides having formula (I) and (I2), a preferred aspect isthat the nitrogenated compounds, in particular having formula (A), aren-hexylamine, n-heptylamine or n-octylamine.

For the mixed oxides of the present invention, the powder X-raydiffraction patterns were measured by means of a vertical goniometerequipped with an electronic pulse height analyzer and using CuKαradiation (λ=1.54178 Å): these diffraction patterns show the presence ofan amorphous phase and a crystalline phase with a monoclinic symmetryisostructural with wolframite, in which the peak positioned at about30.90°±0.5° of 2-theta, corresponding to the convolution of the doubletconsisting of reflections having indexes 111 and 11-1, typical of awolframite-type structure, proves to be the strongest peak.

Other crystalline phases can be present in traces.

Table 1 reports the reflections of the XRD pattern typical of theWolframite structure:

TABLE 1 No 2θ (°) Intensity 1 15.6 ± 0.1 Weak 2 19.3 ± 0.2 Strong 3 24.0± 0.3 Strong 4 24.9 ± 0.3 Strong 5 30.9 ± 0.5 Very Strong 6 31.5 ± 0.5Medium 7 36.7 ± 0.5 Strong 8 37.2 ± 0.5 Weak 9 39.2 ± 0.5 Medium 10 41.7± 0.6 Strong 11 46.5 ± 0.6 Weak 12 48.1 ± 0.6 Very Weak 13 49.1 ± 0.6Weak 14 52.3 ± 0.7 Medium 15 54.7 ± 0.7 Strong 16 58.8 ± 0.7 Very Weak17 62.6 ± 0.7 Medium 18 63.7 ± 0.7 Weak 19 66.0 ± 0.8 Strong 20 68.9 ±0.8 Weak

In the mixed oxides according to the present invention, the resolutionand integrated area of the peaks is in relation to the crystallinitydegree: in all the mixed oxides of the present invention, and thereforealso those with a low crystallinity, for example, lower than 15%, thereflections indicated as very strong or strong in Table 1, indicated inTable 2, can in any case be identified. The mixed oxides according tothe present invention therefore have an XRD pattern characterized by thepresence of an amorphous phase and a crystalline phase with a monoclinicsymmetry isostructural with wolframite whose XRD pattern comprises thereflections indicated in Table 2:

TABLE 2 No 2θ (°) Intensity 1 19.3 ± 0.2 Strong 2 24.0 ± 0.3 Strong 324.9 ± 0.3 Strong 4 30.9 ± 0.5 Very Strong 5 36.7 ± 0.5 Strong 6 41.7 ±0.6 Strong 7 54.7 ± 0.7 Strong 8 66.0 ± 0.8 Strong

The low crystallinity degree can cause a certain shift of thesereflections. The evolution observed with an increase in thecrystallinity degree, however, allows attributing without doubts suchpatterns to materials having a low crystallinity containing a phaseisostructural with wolframite. The resolution of the spectrum increaseswith the increase of the crystallinity degree.

The calculation of the crystallinity degree of the mixed oxidesaccording to the present invention was effected applying the followingprocedure:

-   -   the diffraction peak in the XRD pattern located at about        30.90°±0.5° of 2-theta is selected for the sample considered,        corresponding to the convolution of the doublet consisting of        reflections having indexes 111 and 11-1, typical of the        wolframite-type structure;    -   the relative crystallinity of the sample is calculated applying        the following equation:        Crystallinity=(Ix/Istd)*100        wherein:

-   Ix is the integrated intensity of the peak selected in the X-ray    diffraction pattern of the sample of mixed oxide containing nickel,    molybdenum and tungsten whose relative crystallinity is to be    calculated;

-   Istd is the integrated intensity of the peak selected in the X-ray    diffraction pattern of the same sample of mixed oxide containing    nickel, molybdenum and tungsten, after calcination at 900° C., said    calcined sample proving to be a fully crystalline mixed oxide    isostructural with wolframite.

In order to estimate the crystallinity through X-ray diffraction data ofthe samples of mixed oxide containing nickel, molybdenum and tungsten,the collection of diffraction data must be carried out according to thefollowing criteria:

-   -   a) use of the same diffractometer;    -   b) use of the same weights of the sample whose relative        crystallinity is to be calculated and the same sample calcined        at 900° C. (constant weight);    -   c) use of the same data collection conditions, for example        2-theta-step (preferably 0.03°) and accumulation time        (preferably 20 seconds/step).

The procedure envisages the following phases:

-   a) control of the intensity of the X-ray beam and offset of the    diffractometer through data collection on a standard (for example,    Si (111));-   b) diffraction data collection on the sample of mixed oxide    isostruttural with wolframite containing nickel, molybdenum and    tungsten calcined at 900° C., immediately followed by the collection    of XRD data of the same sample containing nickel, molybdenum and    tungsten whose relative crystallinity is to be calculated.

The calculation of the integrated intensity of the diffraction peak inthe XRD pattern selected must be carried out using the same method forthe sample of mixed oxide containing nickel, molybdenum and tungstenwhose relative crystallinity is to be calculated and for the same samplecalcined at 900° C.

The method involves fitting the profile of the XRD pattern payingparticular attention to the calculation of the background.

Alternatively, the integration of the intensity of the peak can becarried out with the same angular range of 2-theta (before and after thepeak) for both the mixed oxide containing nickel, molybdenum andtungsten whose relative crystallinity is to be calculated and for thesame sample calcined at 900° C.

The mixed oxides OM of the present invention, and, in particular, theoxides having formula (I), (I1) and (I2), characterized in that theycomprise an amorphous phase and a crystalline phase isostructural withwolframite, and having a crystallinity degree higher than 0 and lowerthan 100%, possibly formed without a binder, or in the shaped form witha binder, once transformed into the corresponding sulfides (I)S, (I1)Sand (I2)S, they become catalysts active in hydrotreatment processes, andin particular simultaneous hydrodesulfurization, hydro denitrificationand hydrodearomatization processes.

The sulfidation of the mixed oxides of the present invention and inparticular compounds having formula (I), possibly formed without abinder, or in the shaped form with a binder, for obtaining thecorresponding sulfide compositions which are a further object of thepresent invention and are active as hydrotreatment catalysts, iseffected using any of the techniques and sulfiding agents known toexperts in the field. In particular, the sulfidation can be carried out“ex situ” or “in situ”, i.e. in the same reactor in which thehydrotreatment is subsequently effected. The sulfidation process can becarried out in a reducing atmosphere, for example consisting of H₂S andhydrogen, or CS₂ and hydrogen, at a high temperature, for exampleranging from 300° to 500° C., for a period sufficient for sulfiding thestarting mixed oxide, for example from 1 to 100 hours. Alternatively,the sulfidation can also be carried out using dimethyl disulfidedissolved in a hydrocarbon charge, such as naphtha or gas oil, at atemperature ranging from 300° to 500° C. Finally, the sulfidation can becarried out directly using the sulfur present in the feedstock to betreated, preferably at a temperature ranging from 300° to 500° C.

Sulfidation techniques which can be conveniently used for transformingthe mixed oxides of the present invention into the correspondingsulfides are also described, for example, in “Petroleum Refining”, J. H.Gary, G. E. Handwerk, M. Dekker Ed. 1994.

The mixed oxides OM of the present invention, in particular compoundshaving formula (I), and therefore compounds having formula (I1) and(I2), all useful as precursors of the corresponding sulfide metalliccompositions of the present invention, can be prepared simply andeconomically.

A further object of the present invention therefore relates to a processfor preparing mixed oxides OM according to the present invention,particularly mixed oxides having formula (I), which comprises thefollowing steps:

-   1) preparing a mixture in water of at least one soluble source of    Ni, at least one soluble source of W and a soluble source of Mo, at    least one soluble, hydrolyzable or dispersible source of at least    one element Z and, as nitrogenated compound N, an amine having    formula (A)    R¹R²R³N  (A)    -   wherein R¹ is a linear, branched or cyclic alkyl, containing        from 4 to 12 carbon atoms, and    -   R² and R³, equal to or different from each other, are selected        from H and linear, branched or cyclic alkyl, containing from 4        to 12 carbon atoms, said alkyl possibly being equal to or        different from R¹; wherein the molar ratio N/(Ni+Mo+W) is        greater than and lower than or equal to 1, and is preferably        greater than 0.1-   2) subjecting the mixture to hydrothermal treatment obtaining a    suspension,-   3) recovering from the suspension, the solid contained therein,-   4) subjecting the solid recovered in step (3) to thermal treatment    at a temperature higher than or equal to 150° C. and lower than    900° C. obtaining a mixed oxide OM, containing an amorphous phase    and a wolframite isostructural crystalline phase, having a    crystallinity degree greater than 0 and less than 100%.

According to a preferred aspect, in step (4) a mixed oxide havingformula (I) is obtained.

In step 1, the soluble source of Ni is preferably selected from thecorresponding acetates, hydroxy-carbonates, carbonates,acetylacetonates, and even more preferably is nickel acetate. Thesoluble source of molybdenum and tungsten is preferably selected fromacids, oxides and salts of ammonium. Ammonium heptamolybdate asmolybdenum salt and ammonium metatungstate as tungsten salt, arepreferably used.

When Z is silicon, colloidal silicas, fumed silica and tetra-alkylorthosilicates in which the alkyl group contains from 1 to 4 carbonatoms, can be suitably used as corresponding soluble, dispersible orhydrolyzable compounds.

Hydrolyzable silicas, which, starting from monomeric precursors ofsilicon, guarantee a better dispersion, are preferably used. Tetraethylorthosilicate is more preferably used.

When Z is aluminium, aluminium lactate can be suitably used as solublecompounds and, as corresponding dispersible or hydrolyzable compounds,dispersible aluminas, alumina monohydrates AlOOH, alumnina trihydratesAl(OH)₃, aluminium oxide, aluminium trialkoxides wherein the alkyl islinear or branched and can contain from 2 to 5 carbon atoms.

The dispersible aluminas are preferably bohemites or pseudo-bohemitescharacterized by particles with an average diameter of less than 100microns. Dispersible aluminas which can be suitably used are for examplebohemites of the series Versal®, Pural®, Catapal®, Disperal® andDispal®.

Particularly preferred among dispersible aluminas are aluminasdispersible at room temperature in the presence of stirring in water orin aqueous solution containing a monovalent acid: in the dispersed phasethese aluminas are nanodimensional, characterized by dimensions of thedispersed particles ranging from 10 to 500 nm. Dispersible aluminas ofthis type which can be suitably used are, for example, bohemites of theseries Disperal® and Dispal®.

Hydrolyzable aluminas, which, starting from monomeric precursors ofaluminium, guarantee a good dispersion, are preferably trialkylaluminates in which the alkyl group contains from 3 to 4 carbon atoms.The element Z, selected from Si, Al or mixture thereof, is involved inreaction processes with the other oxidic components of the catalyst,giving rise to the formation of a mixed oxide with four metalliccomponents.

The nitrogenated compounds having formula (A) are preferablyn-hexylamine, n-heptylamine or n-octylamine.

The aqueous mixture is preferably prepared by dissolving the sources ofthe metals Ni, W and Mo in water, preferably in this order, and addingthe source of the element Z to the solution thus obtained. The amine isthen added, obtaining a suspension.

In the mixing step 1, preferably the ratios between the reagents,expressed as molar ratios, are the following:

-   Ni/Mo+W=0.6-1.5,-   Mo/W greater than 0.1 and lower than 10-   R¹R²R³N/(Ni+Mo+W)=0.1-1, more preferably 0.15-0.7    (Ni+Mo+W)/Z greater than or equal to 0.3 and lower than or equal to    10 and preferably ranging from 0.8 to 10-   H₂O/(Ni+Mo+W+Z)≧20, preferably ranging from 30 to 150.

The molar ratio Ni/Mo+W preferably ranges from 0.80 to 1.4, preferablyfrom 0.95 to 1.4, even more preferably from 0.98 to 1.3.

In step (2), the resulting mixture is subjected to hydrothermaltreatment, in a closed reactor, preferably at a temperature ranging from80 to 150° C., preferably from 80 to 100° C., even more preferably at atemperature lower than or equal to that of the lowest-boiling reagent.The hydrothermal treatment is prolonged for a time preferably rangingfrom 5 hours to 3 days. It is preferable to operate under stirring. Aperipheral rate ranging from 10 to 300 m/min is preferably used.

At the end, the suspension obtained is cooled and discharged. The solidis recovered from said suspension, in step (3): the recovery can beeffected using all the solid-liquid separation techniques known toexperts in the field, for example by means of filtration, flash dry, orby feeding the suspension to a spray drier.

The solid recovered consists of an amorphous matrix and some diffractionpeaks of unidentified products, not attributable to the wolframiteisostructural phase, may be present. These peaks are no longer presentin the mixed oxides, object of the present invention obtained afterthermal treatment at a temperature higher than 150° C.

The formation yield of the mixed oxide is higher than 90%, preferablyhigher than 95%, wherein said yield is calculated after removal of theorganic component C. The yield is calculated by normalizing the weightof the mixed oxide thus obtained with respect to the theoretical weightof the oxides present in the reagent mixture, calculated consideringthat all the sources of Ni, Mo, W and the element Z are transformed intothe corresponding oxides.

The filtration, effected according to the known techniques, can usecontinuous filters, such as centrifuges, or non-continuous filters suchas filter presses, pressure filters, vacuum filters. Microfiltrationoperations can be associated to make the recovery of the salts of thetransition metals present in the filtration water, quantitative.Separation by means of spray drying envisages drop atomization of thesuspension which is fed through a nozzle or turbine. A hot carrier gas(generally air or nitrogen) is present in the spray chamber, whichcauses the evaporation of the liquid present in the drops and formationof particles which are recovered by means of a cyclone. The carrier gascan be fed in the same direction as the suspension or in countercurrent.

The temperature of the carrier gas in the inlet ranges from 200 to 700°C., preferably from 300 to 500° C.; the temperature of the carrier gasat the outlet ranges from 50 to 200° C., preferably from 100 to 160° C.

The solid obtained from step (3) can be directly subjected to thermaltreatment. The thermal treatment allows to obtain the formation of thewolframite isostructural crystalline phase.

The choice of temperature at which the thermal treatment is effectedallows to calibrate the crystallinity degree of the resulting mixedoxide.

In particular, thermal treatment at temperatures higher than or equal to150° C. and lower than or equal 500° C., preferably temperatures higherthan or equal to 170° C. and lower than or equal 500° C., allow toobtain a mixed oxide containing an amorphous phase and a wolframiteisostructural crystalline phase, wherein said oxide has a crystallinitydegree greater than 0 and lower than or equal to 70%. During the thermaltreatment at a temperature higher than or equal to 150° C. and lowerthan or equal 500° C., preferably lower than or equal to 500° C. andhigher than or equal to 170° C., the partial transformation of saidnitrogenated compound N into organic residue R can also be obtained: theresulting mixed oxide will therefore have formula (I2) and acrystallinity degree greater than 0 and lower than 70%.

Thermal treatment at temperatures higher than 500° C. and lower than900° C. allows to obtain a mixed oxide containing an amorphous phase anda wolframite isostructural crystalline phase, wherein said oxide has acrystallinity degree greater than 70 and lower than 100%.

At temperatures higher than 500° C. and lower than 900° C., the totalremoval is obtained of the nitrogenated compound N by decomposition: theresulting mixed oxide will therefore have formula (I1) and acrystallinity degree higher than 70% and lower than 100%.

The thermal treatments can be carried out in air, oxygen or nitrogen,for example in thermostatic chambers or muffles, with the possibility ofoperating with a temperature rise, and/or fluidification of the solid tobe treated.

Before the sulfidation phase, the mixed oxide obtained from step (4) mayrequire a forming phase, depending on the type of reactor in which it isused. Normally, the most widely used forming techniques without additionof a binder are pressing, binder-free extrusion, pelletization andagglomeration in spheroidal form by means of spray-drying and dropcoagulation techniques. For this type of application, the mostconvenient technique is extrusion, either with or without a binder. Thistechnique requires the possible addition to the material to be formed,before extrusion and to allow the drawing process of the material, of amineral or organic acid and/or plasticizing agents and/or porogen agentsand/or antifoaming agents and/or dispersing agents and/or surfactantsand/or an organic binder and/or an inorganic oxide which acts as binder.These techniques are known to experts in the field and are described forexample in “Extrusion in Ceramics”, Handle, Frank (Eds.), Springer 2007.

Formed mixed oxides, possibly shaped with a binder, can be prepared bymeans of particular procedures which use the solid recovered from step(3): said solid can be subjected to extrusion in the presence of abinder before being subjected to the thermal treatment step. All bindersknown to experts in the field can be used, and, according to a preferredaspect, a fraction of the suspension is used as a binder, possiblyconcentrated, obtained from the hydrothermal step, possibly togetherwith another binder.

In particular, formed mixed oxides according to the present invention,shaped with a binder, can be prepared as follows:

-   1) a mixture in water is prepared, of at least one soluble source of    Ni, at least one soluble source of W and a soluble source of Mo, at    least one soluble source, hydrolyzable or dispersible, of at least    one element Z and, as nitrogenated compound N, an amine having    formula (A)    R¹R²R³N  (A)    wherein-   R¹ is a linear, branched or cyclic alkyl, containing from 4 to 12    carbon atoms, and-   R² and R³, equal to or different from each other, are selected from    H and linear, branched or cyclic alkyl, containing from 4 to 12    carbon atoms, said alkyl possibly being equal to or different from    R¹;-   wherein the molar ratio N/(Ni+Mo+W) is greater than 0 and lower than    or equal to 1, and is preferably greater than 0.1-   2) the mixture is subjected to hydrothermal treatment obtaining a    suspension,-   3) a soluble, hydrolyzable or dispersible precursor of an oxide MeO    is added to the suspension, and possibly a mineral or organic acid,    mixing, possibly in the presence of heating, for a time sufficient    for obtaining a homogeneous paste having a consistency that is    normally considered suitable for extrusion,-   4) the product obtained from the previous step is extruded,-   5) the extruded product is subjected to thermal treatment at a    temperature higher than or equal to 150° C. and lower than 900° C.    obtaining a mixed oxide OM, containing an amorphous phase and a    wolframite isostructural crystalline phase, having a crystallinity    degree greater than 0 and less than 100%, in a shaped form with a    binder MeO.

According to a preferred aspect, in step (5), a mixed oxide havingformula (I), formed, shaped with a binder, is obtained.

In step (5), the temperature conditions at which the thermal treatmentis effected are those previously described with respect to theobtainment of mixed oxides having formula (I) without a binder, and theyare selected in relation to the crystallinity degree to be obtained. Inparticular, thermal treatments at temperatures higher than or equal to150° C. and lower than or equal to 500° C. allows to obtain a formedmixed oxide, shaped with a binder, containing an amorphous phase and awolframite isostructural crystalline phase, wherein said oxide has acrystallinity degree greater than 0 and lower than or equal to 70%;thermal treatment at temperatures higher than 500° C. and lower than900° C. allows to obtain a formed mixed oxide, shaped with a binder,containing an amorphous phase and a wolframite isostructural crystallinephase, wherein said oxide has a crystallinity degree greater than 70%and lower than 100%.

In step (3), the precursor of the oxide MeO is added in a weight ratiowith the theoretical weight of the oxides of Ni, Mo and W present in thesuspension ranging from 5 to 50% by weight. The acid can be added in aquantity ranging from 0.5 to 8.0 g per 100 g of oxide Meo.

Another particular object of the present invention relates to a processfor preparing mixed oxides having formula (I), formed, and possibly alsoshaped with a binder, which comprises the following steps:

-   1) preparing a mixture in water of at least one soluble source of    Ni, at least one soluble source of Mo and a soluble source of W, at    least one soluble, hydrolyzable or dispersible source of at least    one element Z and, as nitrogenated compound N, an amine having    formula (A)    R¹R²R³N  (A)    -   wherein    -   R¹ is a linear, branched or cyclic alkyl, containing from 4 to        12 carbon atoms, and    -   R² and R³, equal to or different from each other, are selected        from H and linear, branched or cyclic alkyl, containing from 4        to 12 carbon atoms, said alkyl possibly being equal to or        different from R¹; wherein the molar ratio N/(Ni+Mo+W) is        greater than and lower than or equal to 1, and is preferably        greater than 0.1-   2) subjecting the mixture to hydrothermal treatment obtaining a    suspension,-   3) dividing the suspension into two parts (a) and (b), being the    weight ratio (a)/(b) preferably ranging from 1.5 to 20,-   4) recovering the solid from part (a) of the suspension, and    possibly treating it at a temperature ranging from 120 to 200° C.,-   5) concentrating part (b) by evaporation or filtration and mixing it    with the compound recovered in step (4),-   6) extruding the mixture resulting from step (5), possibly after the    addition of a soluble, hydrolyzable or dispersible precursor of an    oxide MeO,-   7) subjecting the extruded product to thermal treatment at a    temperature higher than or equal to 150° C. and lower than 900° C.    obtaining a mixed oxide OM, containing an amorphous phase and a    wolframite isostructural crystalline phase, having a crystallinity    degree greater than 0 and less than 100%, possibly in a shaped form    with the binder MeO.

According to a preferred aspect, in step (7), a mixed oxide havingformula (I), formed, possibly shaped with a binder, is obtained.

In step (4), the recovery of the amorphous compound is effected with thetechniques previously described, for example by means of filtration,flash dry, or by feeding the suspension to a spray drier. If the solidrecovered is treated at a temperature ranging from 120 to 200° C.,before being mixed with part (b) of the suspension, a partialcrystallization of the wolframite isostructural phase can be obtained.

In step (6), if a soluble, hydrolyzable or dispersible precursor of anoxide Meo is added, a mineral or organic acid can also be added.

In step (7), the temperature conditions at which the thermal treatmentis carried out are those previously described with respect to theproduction of mixed oxides having formula (I) without a binder, and theyare selected in relation to the crystallinity degree to be obtained. Inparticular, thermal treatments at temperatures higher than or equal to150° C. and lower than or equal to 500° C. allow to obtain a formedmixed oxide, possibly shaped with a binder, containing an amorphousphase and a wolframite isostructural crystalline phase, wherein saidoxide has a crystallinity degree greater than 0 and lower than or equalto 70%;

thermal treatments at temperatures higher than 500° C. and lower than900° C. allow to obtain a formed mixed oxide, shaped with a binder,containing an amorphous phase and a wolframite isostructural crystallinephase, wherein said oxide has a crystallinity degree greater than 70%and lower than 100%.

The fundamental aspect of this particular procedure, when effectedwithout the addition of any oxide precursor MeO, consists in the absenceof any binder that can alter the composition and physico-chemicalproperties of the oxide precursor, and consequently of the finalcatalyst.

The oxide MeO, when present, acts as binder, and is a preferred aspectthat said oxide MeO be silicon oxide or aluminium oxide, and even morepreferably an oxide of the same element Z present in step 1. When Me isaluminium or silicon, hydrolyzable or dispersible sources of oxide MeOwhich can be suitably used in this forming process are the same used forthe element Z in the preparation phase of the mixed oxide. When Me issilicon, for example, colloidal silicas, fumed silica and tetra-alkylorthosilicates in which the alkyl group contains from 1 to 4 carbonatoms, can be suitably used as corresponding soluble, dispersible orhydrolyzable compounds. When Me is aluminium, alumina monohydratesAlOOH, alumina trihydrates Al(OH)₃, aluminium oxide, dispersiblealuminas, aluminium trialkoxides wherein the alkyl is linear or branchedand can contain from 2 to 5 carbon atoms, can be suitably used.

The dispersible aluminas are preferably bohemites or pseudo-bohemitescharacterized by particles with an average diameter of less than 100microns. Dispersible aluminas which can be suitably used are for examplebohemites of the series Versal®, Pural®, Catapal®, Disperal® andDispal®.

Among dispersible aluminas, aluminas dispersible at room temperature inthe presence of stirring in water or in aqueous solution containing amonovalent acid, are preferably used: in the dispersed phase thesealuminas are nanodimensional, characterized by dimensions of thedispersed particles ranging from 10 to 500 nm. Dispersible aluminas ofthis type which can be suitably used are in particular bohemites of theseries Disperal® and Dispal®.

Mineral or organic acids, when used, can be:

-   -   acids already contained in the dispersible or hydrolyzable        precursor of the oxide MeO, such as for example acetic acid,        nitric acid,    -   acids added directly to the mixture to be extruded, for example        acetic acid, nitric acid, phosphoric acid or boric acid.

In the extrusion step of the procedures described above, plasticizingagents can also be added, such as stearin, glycerin, polyethyleneglycol,porogen agents, such as for example, soluble starch, antifoaming agents,such as for example, silicon and non-silicon formulates, dispersingagents, such as for example, polymer dispersants for ceramic materials,surfactants, such as for example, ionic and non-ionic surface-activeagents, organic ligands such as methocel.

If, when using the procedures described above, a suitable oxideprecursor MeO is added, at the end of the forming process a compositioncontaining a mixed oxide in the shaped form with a binder is obtained.

Said composition contains:

-   -   the binder MeO, in a quantity preferably higher than 5% and        lower than or equal to 50% by weight with respect to the weight        of the mixed oxide, even more preferably from 5 to 30% by weight        with respect to the weight of the mixed oxide, and wherein said        oxide MeO is preferably aluminium oxide or silicon oxide, and        even more preferably is an oxide corresponding to the element Z        contained in the mixed oxide,    -   a mixed oxide according to the invention, essentially having the        same crystallinity, porosity, surface area and structure        characteristics as the corresponding mixed oxide without a        binder.

The mechanical characteristics of the extruded products thus obtainedare suitable for sustaining both the sulfidation phase andthermo-mechanical stress during its use.

The catalysts of the present invention obtained by sulfidation of themixed oxides OM, in particular oxides having formula (I), possiblyformed without a binder, or mixed oxides OM, in particular mixed oxideshaving formula (I), in the form shaped with a binder, are extremelyactive catalysts and stable in hydrotreatment processes and can besuitably used in all refining processes in which hydrotreatmentoperations must be effected, and in particular for obtaining thehydrodesulfurization, hydrodenitrogenation and/or hydrodearomatizationof a hydrocarbon mixture.

A further object of the present invention therefore relates to a processfor the hydrotreatment of a feedstock containing one or morehydrocarbons which comprises putting in contact said feedstock withhydrogen and with the catalysts of the present invention obtained bysulfidation of the mixed oxides OM, in particular mixed oxides havingformula (I), possibly formed.

Any feedstock or hydrocarbon mixture containing sulfur or nitrogenimpurities can be treated with the catalysts of the present invention:oil distillates, oil residues, naphtha, light cycle oil, atmospheric gasoil, heavy gas oil, lube oil, paraffinic base oils, oils from naphthenicdistillates, EST process products, for example, can be subjected totreatment.

EST process products refer, for example, to products obtained from theprocesses described in patent applications MI95A001095, MI01A001111,MI01A001438, MI02A002713, MI03A000692, MI03A000693, MI03A002207,MI04A002445, MI04A002446, MI06A001512, MI06A001511, MI07A001302,MI07A001303, MI07A001044, MI07A001045, MI07A001198, MI08A001061.

With the catalysts of the present invention, it is possible to treathydrocarbon cuts containing up to 40,000 ppm of sulfur, possiblycontaining up to 2,000 ppm of nitrogen. In these cuts, up to 60% byweight of aromatic compounds and up to 30% by weight of PNA can bepresent.

It is preferable to operate at a temperature ranging from 100 to 450°C., preferably from 300 to 370° C., at a pressure ranging from 50 to 100bar, preferably from 50 to 70 bar. The WHSV ranges from 0.5 to 10hours⁻¹, preferably from 1 to 2 hours⁻¹. The quantity of hydrogen canvary from 100 to 800 times the quantity of hydrocarbons, expressed asNlH₂/1 of hydrocarbon mixture.

According to another aspect, the sulfide catalysts of the presentinvention can be used for treating hydrocarbon cuts that have alreadyundergone hydrodesulfurization and hydrodenitrogenation treatment, orcuts that by their nature have a content of S and N sufficiently low,but they are cuts with a high content of aromatic compounds and forwhich this content must therefore be reduced, particularly the contentof polyaromatic compounds (PNA). In particular, due to their highactivity in the hydrodearomatization and reduction of polycyclicaromatic compounds (PNA), the catalysts of the invention can be used inprocesses for the production of white oils from paraffinic base oils orfrom naphthene distillates. They can be particularly used for theconversion of white oils for technical use in white oils for use in foodor medicines, in which the aromatic compounds must be present in atotally minimum quantity or in traces.

The same conditions used for the hydrotreatment can be adopted for thehydrodearomatization.

Due to their capacity of contemporaneously exerting a highhydrodesulfurization, hydrodenitrogenation activity and inhydrodearomatization reactions and in the reduction of aromaticpolycyclic compounds (PNA), the catalysts of the invention can also beconveniently used as hydrogenating component, associated with an acidcomponent, in hydrocracking processes. Feedstocks suitable forhydrocracking are, for example, heavy and extra-heavy crude oils, vacuumgas oil (VGO), vacuum residues (VR).

The synthesis processes of the oxide precursors of the catalysts andcatalytic tests are described in the following examples, which should inno way be considered as limiting the invention itself.

Example 1

The following products were dissolved in order in 450 g of water:

-   43.36 g of Ni(CH₃COO)₂.4H₂O,-   21.58 g of (NH₄)6H₂W₁₂O₄₁.H₂O,-   15.38 g of (NH₄)6Mo₇O₂₄.4H₂O.

A solution is obtained.

After 5 minutes, 65.00 g of a dispersion of Disperal P3 previouslyprepared as described: 12.50 g of Disperal P3 Sasol at 67.8% of Al₂O₃are added to 70.84 g of an aqueous solution at 0.6% by weight of aceticacid.

26.64 g of octylamine are slowly added, obtaining a suspension which ischarged into an autoclave equipped with an anchor stirrer and subjectedto hydrothermal treatment at 98° C. for 18 hours, at a stirring rate of70 m/min. At the end, the autoclave is cooled and the dischargedsuspension is fed to the spray drier (LAB PLANT SD-04). The suspensionis fed with a flow-rate of 8 l/hour. The temperature of the carrier gas(air) at the inlet is maintained at 350° C., the temperature of thecarrier gas at the outlet ranges from 130 to 110° C.

A solid is obtained, which is used in the following examples.

Example 2

A part of the solid obtained in Example 1 is calcined at 900° C. Thediffraction pattern, shown in FIG. 1a , indicates the presence ofwolframite and traces of alpha-NiMoO₄. The diffraction pattern, shown inFIG. 1a , was used for defining the 100% of crystallinity.

Said sample, used for defining the 100% of crystallinity, has an XRDpattern characterized by the signals indicated in the following table:

TABLE 1 No 2θ (°) Intensity 1 15.6 Weak 2 19.3 Strong 3 24.0 Strong 424.9 Strong 5 30.9 Very Strong 6 31.5 Medium 7 36.7 Strong 8 37.2 Weak 939.2 Medium 10 41.7 Strong 11 46.5 Weak 12 48.1 Very Weak 13 49.1 Weak14 52.3 Medium 15 54.7 Strong 16 58.8 Very Weak 17 62.6 Medium 18 63.7Weak 19 66.0 Strong 20 68.9 Weak

The sample is therefore the wolframite isostructural mixed oxidecontaining nickel, molybdenum and tungsten used as reference forestimating the crystallinity through powder X-ray diffraction (XRD) ofthe samples of mixed oxide containing nickel, molybdenum and tungstenobtained in the following examples.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.5)W_(0.5)Al_(0.75)O_(5.125).

Example 3

A part of the solid obtained in Example 1 is subjected to thermaltreatment at 170° C. for 5 hours. The diffraction pattern, shown in FIG.1b , indicates, in addition to the presence of the amorphous phase, thepresence of wolframite having a low crystallinity.

The relative crystallinity, evaluated through powder X-ray diffraction,by means of the procedure previously described, is equal to 9%.

The organic component, calculated from the weight loss between 200 and600° C., measured by means of TGA, is 10.3% by weight.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.5)W_(0.5)Al_(0.75)O_(5.125) and contains 10.3% by weightof organic component with respect to the total weight.

Example 4

A part of the solid obtained in Example 1 is subjected to thermaltreatment at 200° C. for 5 hours. The diffraction pattern, shown in FIG.1c , indicates, in addition to the presence of the amorphous phase, thepresence of wolframite and traces of α-NiMoO₄. The relativecrystallinity, evaluated through powder X-ray diffraction, by means ofthe procedure previously described, is equal to 17%.

The organic component, calculated from the weight loss between 200 and600° C., measured by means of TGA, is 7.5% by weight.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.5)W_(0.5)Al_(0.75)O_(5.125) and contains 7.5% by weight oforganic component with respect to the total weight.

Example 5

A part of the solid obtained in Example 1 is subjected to thermaltreatment at 300° C. for 5 hours. The diffraction pattern, shown in FIG.1d , indicates, in addition to the presence of the amorphous phase, thepresence of wolframite and traces of α-NiMoO₄. The relativecrystallinity, evaluated through powder X-ray diffraction, by means ofthe procedure previously described, is equal to 19%.

The organic component, calculated from the weight loss between 200 and600° C., measured by means of TGA, is 5.5% by weight.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.5)W_(0.5)Al_(0.75)O_(5.125) and contains 5.5% by weight oforganic component with respect to the total weight.

Example 6

A part of the solid obtained in Example 1 is subjected to thermaltreatment at 400° C. for 5 hours. The diffraction pattern, shown in FIG.1e , indicates, in addition to the presence of the amorphous phase, thepresence of wolframite and traces of α-NiMoO₄. The relativecrystallinity, evaluated through powder X-ray diffraction, by means ofthe procedure previously described, is equal to 20%.

Upon analysis by means of adsorption/desorption nitrogen isotherms at 77K, it has a surface area of 124 m²/g, a pore volume of 0.28 ml/g, anaverage pore diameter of 5.4 nm. The organic component, calculated fromthe weight loss between 200 and 600° C., measured by means of TGA, is2.3% by weight.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.6)W_(0.6)Al_(0.76)O_(6.125) and contains 2.3% by weight oforganic component with respect to the total weight. Analyzing thediffraction pattern of FIG. 1e , it is possible to observe that thereare no intense peaks at approximately 46° and 67° of 2-theta, where themost intense reflections of the gamma-alumina are located, as clearlyevidenced in FIG. 3 where the XRD pattern of the sample Disperal P3treated at 400° C. for 5 hours is reported: the XRD pattern shown inFIG. 3 of said sample of calcined Disperal P3 clearly shows that it isconstituted by gamma-alumina phase.

The absence of transition phases of alumina in the sample obtained inthis example is also confirmed by the ²⁷Al MAS NMR analysis (FIG. 4,line a). The spectrum shows only the presence of a peak in the regionwhere aluminium in octahedral coordination (AlO₆) is expected toresonate (maximum at −3.8 ppm), while, on the contrary, is not observedthe presence of signals in the region of chemical shift where usuallyresonate the Al atoms in tetrahedral coordination.

In the case of gamma-alumina, obtained by thermal treatment of thesample Disperal P3 at 400° C., it is clearly evident (FIG. 4, line b)that in addition to a peak assigned to octahedral aluminium (maximum at8.8 ppm), a peak attributed to aluminium in tetrahedral coordination(AlO₄) is present (maximum at 66.3 ppm).

In summary, the configuration of aluminium atoms found in the mixedoxide of the present invention thus differs from that observed in thesample of alumina thermally treated at the same temperature. Thealuminium is then present in the two materials in different forms,showing that the aluminium present in the mixed oxide of the presentinvention, added during synthesis as Disperal P3, is involved inreaction processes with the other oxidic components of the catalyst,giving rise to the formation of a mixed oxide with four metalliccomponents.

Example 7

A part of the solid obtained in Example 1 is subjected to thermaltreatment at 450° C. for 5 hours. The diffraction pattern, shown in FIG.1f , indicates, in addition to the presence of amorphous, the presenceof wolframite (prevalent) and α-NiMoO₄. The relative crystallinity,evaluated through powder X-ray diffraction, by means of the procedurepreviously described, is equal to 38%.

The organic component, calculated from the weight loss between 200 and600° C., measured by means of TGA, is 0.8% by weight.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.5)W_(0.5)Al_(0.75)O_(5.125) and contains 0.8% by weight oforganic component with respect to the total weight.

Example 8

A part of the solid obtained in Example 1 is subjected to thermaltreatment at 500° C. for 5 hours. The diffraction pattern, shown in FIG.1g , indicates, in addition to the presence of amorphous, the presenceof wolframite and traces of α-NiMoO₄. The relative crystallinity,evaluated through powder X-ray diffraction, by means of the procedurepreviously described, is equal to 70%.

The organic component, calculated from the weight loss between 200 and600° C., measured by means of TGA, is 0.6% by weight.

The solid obtained has the following molar compositionNi_(1.0)Mo_(0.5)W_(0.5)Al_(0.75)O_(5.125) and contains 0.6% by weight oforganic component with respect to the total weight.

Example 9 Comparative

The synthesis as described in Example 1 is repeated but withouteffecting the hydrothermal treatment. After the addition of octylamine,the suspension is left under static conditions for 20 hours at roomtemperature. It is then fed to the spray drier. The atomizationconditions are selected so as to guarantee a temperature at the outletof 120° C.

The solid obtained is calcined at 400° C. Upon analysis by means ofadsorption/desorption nitrogen isotherms at 77 K, it has a surface areaof 141 m²/g, a pore volume of 0.25 ml/g, an average pore diameter of 6.0nm.

The diffraction pattern, shown in FIG. 2, reveals the presence ofabundant amorphous+WO₃+α-NiMoO₄+MoO₃+traces of wolframite.

The hydrothermal treatment before drying with a spray drier is thereforefundamental for guaranteeing the mixed oxides according to the presentinvention, avoiding the preferential crystallization of α-NiMoO₄ andsegregated Mo and W oxides.

Example 10 Comparative

7.56 g of octylamine are dissolved in 40 g of absolute ethanol (solutionA). A solution consisting of 14.89 g of nickel nitrate hexahydrate(NiNO), 4.52 g of ammonium heptamolybdate (EMA) and 6.98 g of ammoniummetatungstate hydrate (MTA) dissolved in 50 ml of an aqueous solcontaining 14.90 g of an aqueous dispersion of bohemite (Disperal® P2 ofSasol™) at 10% by weight (solution B) is then added under stirring tosolution A. The molar ratio octylamine/(Ni+Mo+W) is equal to 0.6. Alight green gel is formed, which is left under stirring for 3 hours,heating to 70° C. It is left to rest for 48 hours. The gel obtained doesnot have a supernatant and is dried in an oven at 90° C. for 48 hours.The dried material is subjected to thermal treatment at 400° C. for 5hours in air.

The solid has the following molar composition:Ni_(0.05)Mo_(0.03)W_(0.03)Al_(0.03)O_(0.28) and contains 2.0% by weightof organic residue with respect to the total weight of the solid. Thespecific surface area is 151 m²/g, the total pore volume 0.381 cm³/g,the average pore diameter 6.3 nm, calculated from the desorptionisotherm.

Example 11 Catalytic Test

The hydrotreatment catalytic test was carried out as describedhereunder.

The fixed bed reactor is charged with 5 grams of catalyst previouslypressed and granulated (20-40 mesh).

The process takes place in 2 phases: sulfidation of the catalyst andhydrotreatment step.

-   a) Sulfidation

The catalyst is treated with a sulfiding mixture consisting of StraightRun Gasoil, with the addition of Dimethyldisulfide, so as to have aconcentration of S equal to 2.5 by weight with respect to the totalweight of the sulfiding mixture. The sulfidation conditions used are:

-   LHSV=3 hours'-   P=30 bar-   T=340° C.-   H₂/sulfiding mixture=200 Nl/1.-   b) Hydrotreatment

The reaction is carried out under the following conditions:

-   T=340 ° C.-   P=60 bar-   Liquid feedstock flow-rate: 8 ml/hour-   H₂ flow-rate: 5 Nl/hour-   WHSV=1.35 hour′

The feedstock stream consists of gasoil coming from thermal cracking andcontains 23900 ppm of sulfur, 468 ppm of nitrogen, 37.6% by weight oftotal aromatics and 17% by weight of PNA.

The activity of the catalysts is evaluated after 150 hours of test at340° C. and is expressed as hydrodenitrogenation (HDN),hydrodesulfurization (HDS), hydrodearomatization (HDA) conversion and asPNA conversion.

The catalyst of comparative Example 10 was subjected to the catalytictest. For this catalyst, the hydrodenitrogenation (HDN),hydrodesulfurization (HDS), hydrodearomatization (HDA) conversion andreduction of PNA are defined as being equal to 100.

Example 12

The sample of Example 3 was subjected to the catalytic test as describedin Example 11. The results obtained are normalized with respect to thoseobtained with the catalyst of comparative Example 10.

The data are indicated in the following table:

Example Catalyst HDN HDS HDA PNA 11 Comparative Ex. 10 100 100 100 10012 Example 3 101 102 231 104

As can be observed from the data indicated above, the mixed oxides ofthe present invention characterized in that they comprise an amorphousphase and a wolframite isostructural crystalline phase, having acrystallinity degree higher than 0 and lower than 100%, allow to obtainbetter performances for all the conversion parameters considered, withrespect to the comparative material, representative of the prior art. Inparticular, they are more active in the hydrodearomatization activityand reduction of PNA.

Example 13

The sample of comparative Example 9 was subjected to the catalytic testas described in Example 11. The results obtained are normalized withrespect to those obtained with the catalyst of comparative Example 10.

The catalyst 9 has a reduction in the hydrodenitrogenation conversion(C_(HDN)=96%) and hydrodesulfurization conversion (C_(HDS)=98%) withrespect to the comparative catalyst 10, and therefore also with respectto the catalyst of Example 3, representative of the invention.

As can be observed from the data indicated, the samples in which themixed oxide tends to form different crystalline phases (e.g.WO₃+alfa-NiMoO₄+MoO₃), are less active with respect to the mixed oxidesof the present invention, characterized in that they comprise anamorphous phase and a wolframite isostructural crystalline phase, havinga crystallinity degree higher than 0 and lower than 100%.

The invention claimed is:
 1. Mixed oxides comprising formula (I):Ni_(a) Y_(b) Z_(c) O_(d) .pC  (I) possibly formed without a binder,wherein Y is a mixture of Mo and W in a molar ratio Mo/W greater than0.1 and less than 10, Z is selected from Si, Al and mixtures thereof, Ois oxygen, C is an organic component selected from a nitrogenatedcompound N, an organic residue R containing carbon and nitrogen, and amixture of the residue R and nitrogenated compound N, said nitrogenatedcompound N being an amine having formula (A)R¹R²R³N  (A) wherein R¹ is a linear, branched or cyclic alkyl,containing from 4 to 12 carbon atoms, and R² and R³, equal to ordifferent from each other, are selected from H and linear, branched orcyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl possiblybeing equal to or different from R¹, a, c and d are the number of molesof Ni, Z, and O, respectively, b is the sum of the moles of W and Mo pis the weight percentage of C with respect to the total weight of thecompound having formula (I), a, b, c, and d are greater than 0 a/b isgreater than or equal to 0.6 and lower than or equal to 1.5, (a+b)/c isgreater than or equal to 0.3 and lower than or equal to 10,d=(2a+6b+Hc)/2 whereinH=4 when Z=SiH=3 when Z=Al and p is greater than or equal to 0 and lower than orequal to 40%, wherein said mixed oxides of formula (I) are characterizedin that their diffraction patterns show the presence of an amorphousphase and a wolframite isostructural monoclinic crystalline phase, whoseXRD pattern comprises the reflections indicated in the following table:No 2θ (°) 1 19.3 ± 0.2 2 24.0 ± 0.3 3 24.9 ± 0.3 4 30.9 ± 0.5 5 36.7 ±0.5 6 41.7 ± 0.6 7 54.7 ± 0.7 8 66.0 ± 0.8

the crystallinity degree of said mixed oxides being greater than 0 andlower than 100%.
 2. The mixed oxides according to claim 1, comprising anamorphous phase and a wolframite isostructural crystalline phase havinga crystallinity degree greater than 70% and lower than 100%, havingformula (I1):Ni_(a)Y_(b)Z_(c)O_(d)  (I1) possibly formed without a binder, wherein Yis a mixture of Mo and W in a molar ratio Mo/W greater than 0.1 and lessthan 10, Z is selected from Si, Al and mixtures thereof, O is oxygen, a,c, and d are the number of moles of Ni, Z, and O, respectively, and aregreater than 0 b is the sum of the moles of W and Mo, and is greaterthan 0 a/b is greater than or equal to 0.6 and lower than or equal to1.5, (a+b)/c is greater than or equal to 0.3 and lower than or equal to10, d=(2a+6b+Hc)/2 whereinH=4 when Z=SiH=3 when Z=Al.
 3. The mixed oxides according to claim 1, comprising anamorphous phase and a wolframite isostructural crystalline phase havinga crystallinity degree greater than 0 and lower than or equal to 70%,having formula (I2):Ni_(a)Y_(b)Z_(c)O_(d).pC  (i2) possibly formed without a binder, whereinY is a mixture of Mo and W in which the molar ratio Mo/W is greater than0.1 and less than 10, Z is selected from Si, Al and mixtures thereof, Ois oxygen, C is an organic component selected from a nitrogenatedcompound N, an organic residue R containing carbon and nitrogen, and amixture of the residue R and nitrogenated compound N, said nitrogenatedcompound N being an amine having formula (A)R¹R²R³N  (A) wherein R¹ is a linear, branched or cyclic alkyl,containing from 4 to 12 carbon atoms, and R² and R³ , equal to ordifferent from each other, are selected from H and linear, branched orcyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl possiblybeing equal to or different from R¹, a, c and d are the number of molesof Ni, Z, O, respectively, b is the sum of the moles of W and Mo p isthe weight percentage of C with respect to the total weight of thecompound having formula (I2), a, b, c, and d are greater than 0 a/b isgreater than or equal to 0.6 and lower than or equal to 1.5, (a+b)/c isgreater than or equal to 0.3 and lower than or equal to 10, d=(2a+6b+Hc)/2 whereinH=4 when Z=SiH=3 when Z=Al p is greater than 0 and lower than or equal to 40%.
 4. Themixed oxides of claim 1, in a shaped form with a binder.
 5. The mixedoxides according to claim 1, wherein Y is a mixture of Mo and W in aMo/W molar ratio ranging from 0.2 to
 9. 6. The mixed oxides according toclaim 1, wherein a/b ranges from 0.80 to 1.4.
 7. The mixed oxidesaccording to claim 6, wherein a/b ranges from 0.98 to 1.3.
 8. The mixedoxides according to claim 1, wherein the organic component C is greaterthan 0 and less than or equal to 25% by weight.
 9. The mixed oxidesaccording to claim 1, wherein the crystallinity degree is greater thanor equal to 3% and less than 100%.
 10. The mixed oxides according toclaim 9, wherein the crystallinity degree is greater than or equal to 6%and less than or equal to 90%.
 11. The mixed oxides according to claim3, wherein the crystallinity degree is greater than or equal to 3% andless than or equal to 70%.
 12. The mixed oxides according to claim 1,wherein R is obtained from the nitrogenated compound N by means ofthermal treatment.
 13. The mixed oxides according to claim 1, whereinthe nitrogenated compounds N having formula (A) are n-hexylamine,n-heptylamine or n-octylamine.
 14. The mixed oxides according to claim1, having an XRD pattern characterized by the presence of an amorphousphase and a crystalline phase with a wolframite isostructural monoclinicsymmetry, wherein the peak positioned at about 30.90°±0.5° of 2-theta isthe most intense peak.